Patentamt

J E u r o p European
a i s c h e sPatent Office © Publication number: 0 1 1 9 41 4

Office europeen des brevets B 1

§) EUROPEAN PATENT SPECIFICATION

(jjj) int. CI.4: C 08 F 2 2 2 / 0 8 , C 08 F 8 / 3 6

© Dateof publication of patent specification: 01 .06.88
J) Application number: 84100963.2
® Date of filing: 31.01.84

® Preparation of low molecular weight styrene-maleic anhydride copolymers and sulfonated copolymers
thereof.

(D Priority: 22.02.83 US 468256 (73) Proprietor: National Starch and Chemical

Corporation
Box 6500
(§) Dateof publication of application: Bridgewater, N.J. 08807 (US)
26.09.84 Bulletin 84/39
(72) Inventor: Chiao,WenB.
(§) Publication of the grant of the patent: 6 Welles Court
01.06.88 Bulletin 88/22 Piscataway New Jersey 08854 (US)
Inventor: Ray-Chaudhuri, Dilip K.
484 Rolling Hills Road
(ffi) Designated Contracting States: Bridgewater New Jersey 08807 (US)
BE DE FRGBITNL
(74) Representative: Hagemann, Heinrich, Dr. et al
(jj§) References cited: Patentanwalte GEYER, HAGEMANN &
EP-A-0007 044 PARTNER Postfach 860329
DE-A-1 930 217 D-8000 Miinchen 86 (DE)
US-A-2 606 891
US-A-3 085 994
CD

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
Ul paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington Spa, England.
 0 119 414
Description

This invention relates to an improved process for preparing a copolymer of styrene and maleic
anhydride monomers in the molecular weight range of 500 to 10,000 in a solvent. Upon completion of the
5 polymerization reaction, the copolymer can thereafter be sulfonated in the solvent used in the
polymerization reaction in a continuous process to yield the corresponding sulfonated copolymer.
The copolymerization of styrene and maleic anhydride is well known in the art. See, for example,
US— A—2,675,370; US —A—3,085,994, US— A—3,178,395 and US— A—3,730,900. A process of
precipitation polymerization may be employed whereby a solvent is chosen for the reaction which is inert
io to the polymerization reaction conditions and in which both reactants are soluble. The reactants polymerize
at a concentration of 10 to 50% in the solvent at elevated temperatures. Various free radical generating
catalysts including organic peroxides and azo compounds are employed for the polymerization. After the
polymerization is complete and the mixture is cooled, the resultant copolymer precipitates from the
selected solvent and is recovered by filtration and then dried. Various solvents which have been used in
75 precipitation polymerization include toluene, benzene, and xylene. A polymerization process yielding
copolymers which remain soluble in the polymerization solvent may also be achieved employing similar
reaction conditions. Acceptable solvents for this process include ketones and esters such as acetone,
methyl ethyl ketone and butyl acetate, dioxane, carbon tetrachloride and 1,2-dichloroethane. In order to
prepare a copolymer of sufficiently low molecular weight to render it soluble in these solvents, a chain
20 transfer agent must be used.
The preparation of sulfonated styrene-maleic anhydride copolymers is also known. In
US—A—3,072,619 the sulfonation reaction involves uniformly dissolving styrene-maleic anhydride
copolymer in a liquid chlorinated aliphatic hydrocarbon and then treating the solution with a sulfur
trioxide-organic complex. The sulfonated copolymer precipitates from solution and is thus easily
25 recoverable by conventional techniques such as decanting, filtering, or centrifuging. Suitable solvents for
the sulfonation reaction include methylene chloride, carbon tetrachloride and 1,2-di-chloroethane.
In order to obtaion copolymers of low molecular weight, various conventional solvents which possess
chain-terminating capabilities, e.g. alkyi substituted aromatic organic compounds in which the alkyl
substituent provides an active hydrogen atom (cumene and cymene), are used in the polymerization
30 process. See US— A—3,085,994 (cited previously); US— A—3,388,106, and US— A—3,451,979; describing
the precipitation polymerization of styrene and maleic anhydride.
In some instances, however, conventional solvents with chain-terminating capabilities may be
inadequate in preparing such low molecular weight copolymers and use of chain transfer agents, as
mentioned above, is required. A variety of chain transfer agents, for example, polyhalides, disulfide
35 compounds, and mercaptans are known in the literature. While various mercaptans are known to regulate
molecular weight distribution efficiently producing uniform products, mercaptans possess an undesirable
strong odor which most often remains with the polymerized end-product. In the US—A—2,606,891
describes the use of mercaptans containing 5 to 12 carbon atoms as effective chain transfer agents in
styrene-maleic anhydride polymerization reactions. Mercaptan levels of 5 to 25% based on the weight of
40 the monomers are suggested for the reaction. While the most efficient mercaptans are those of low
molecular weight, the US—A—2,606,891 does not suggest use of C, to C4 mercaptans due to their
undesirable strong odor.
It should be noted that when a mercaptan of increasing chain length is used in the polymerization
reaction, proportionately more will be required to produce a low molecular weight copolymer due to the
45 decreasing efficiency of the mercaptan. As the chain length of a mercaptan decreases, less mercaptan will
be required to produce a similar low molecular weight copolymer. Unfortunately, the copolymer will be
expected to possess an objectionable mercaptan odor if the mercaptan contains less than 5 carbon atoms.
Therefore, in order to avoid the odor problem created by short chain mercaptans, large quantities of less
efficient long chain mercaptans must be employed in the polymerization reaction.
so In spite of the abundant general teachings directed to preparing low molecular weight copolymers of
styrene and maleic anhydride employing chain-terminating solvents and chain transfer agents, no process
is known for producing such copolymers conveniently and efficiently with short chain mercaptans where
the resultant copolymer possesses a minimum or imperceptible amount of odor. Because of the increased
efficiency afforded by short chain mercaptans in the polymerization reaaction mentioned above, a process
55 for the production of styrene-maleic anhydride copolymers is desired using such mercaptans where the
end-products process no odor problem. The process described in the EP—A—7044 is directed to the
production of speck-free, carboxylated rubber latices by emulsion polymerization carried out above 50°C in
the substantial or complete absence of emulsifiers and in the presence of peroxodisulphate and a
mercaptocarboxylic acid of from two to six carbon atoms and/or water-soluble salts thereof.
60 Thus, there is a need for a process for preparing a copolymer of styrene or substituted styrene and
maleic anhydride in a solvent such that the resultant copolymer has a molecular weight in the range of 500
to 10,000 and is substantially odorless. There is also a need for a convenient and efficient process for
preparing a sulfonated copolymer of styrene or substituted styrene and maleic anhydride using the same
solvent for the sulfonation as was used for the polymerization such that the resultant sulfonated copolymer
65 is substantially odorless.

2
 ) 119 414

The present invention provides an improved process for preparing a copolymer ot styrene ana maieic
inhydride in the molecular weight range of 500 to 10,000 by polymerizing styrene and maleic anhydride
nonomers in a molar ratio of 1:1 to 9:1 in 1,2-dichloroethane at 70°— 100°C in the presence of a free radical
jenerating polymerization catalyst and a mercaptan chain transfer agent, characterized in that the
jolymerization is carried out in the presence of 0.5 —5%, based on the weight of the monomers, of 3-
nercaptopropionic acid or methyl-3-mercaptopropionate as the chain transfer agent, whereby a
substantially odorless copolymer which remains soluble in the 1,2-dichloroethane results.
It also provides an improved process for preparing a sulfonated copolymer of styrene and maleic
anhydride by polymerizing styrene and maleic anhydride monomers in a molar ratio of 1:1 to 9:1 in 1,2-
iichloroethane at 70°— 100°C in the presence of a free radical generating polymerization catalyst and a
nercaptan chain transfer agent yielding a copolymer in the molecular weight range of 500 to 10,000,
sulfonating the resulting copolymer of styrene and maleic anhydride in the 1,2-dichloroethane, and
ecovering the resultant precipitated sulfonated copolymer, characterized in that the polymerization as
:arried out in the presence of 0.5—5%, based on the weight of the monomers, of 3-mercaptopropionic acid
jr methyl-3-mercaptopropionate as the chain transfer agent, whereby a substantially odorless and soluble
copolymer of styrene and maleic anhydride is formed and results in a substantially odorless copolymer
after sulfonation.
The preferred styrene to maleic anhydride molar ratio is from 1:1 to 3:1. The molecular weight of the
;opolymer herein will range from 500 to 10,000, preferably 1,000 to 4,000. The resultant low molecular
weight styrene-maleic anhydride copolymer does not precipitate, but remains soluble in 1,2-
dichloroethane and can thereafter be conveniently sulfonated by conventional methods. Unexpectedly,
30th the styrene-maleic anhydride copolymer as well as the sulfonated copolymer are substantially
Ddorless.
The styrene or substituted monomers useful in the invention include styrene, a-methyl styrene, and
/inyl toluene. As used herein, styrene is intended to include both styrene and the above-mentioned
substituted styrenes.
The present invention provides an efficient process for preparing styrene-maleic anhydride
;opolymers. Moreover, due to the solubility of the copolymer in 1,2-dichloroethane, it offers a convenient
and step-saving process for producing sulfonated copolymers with the elimination of intermediate
recovery, purification, and handling steps involved in the general styrene-maleic anhydride polymerization
process before the sulfonation reaction.
The preferred amount of 3-mercaptopropionic acid and methyl-3-mercaptopropionate used is 1—3%.
It should be noted that mixtures of these specified mercaptans may also be employed in the amounts
mentioned above in the polymerization reaction.
The polymerization reaction will require a free-radical generating catalyst to initiate the reaction.
Suitable catalysts in accordance with the process include many organic peroxides, for example, benzoyl
peroxide, acetone peroxide, and cumene hydrogen peroxide, and azo compounds such as
azoisobutyronitrile and 2,2'-azobis (2-methyl-pentanenitrile). The use of azoisobutyronitrile or 2,2'azobis
(2-methyl-pentanenitrile) in an amount of 4—6%, based on the weight of the styrene and maleic anhydride
monomers, is preferred.
The monomers should be polymerized in sufficient 1,2-dichloroethane to ensure adequate monomer
dispersion and to maintain the final copolymer in solution. The monomers will polymerize satisfactorily in
1,2-dichloroethane at a concentration of 10 to 50% in the solvent. The reaction is preferably conducted at a
monomer concentration of about 20% in the solvent.
The amount of mercaptan chain transfer agent employed in the polymerization process is largely
dependent upon the molar ratio of the monomers. The reactivity of the polymerization increases as the
amount of maleic anhydride in the reaction increases, thus rendering larger molecular weight copolymers
at a faster rate. Also, due to the polarity maleic anhydride imparts to the copolymer, as the amount of
maleic anhydride in the reaction increases, copolymers may be produced which are less soluble in the
dichloroethane solvent. Therefore, when larger amounts of maleic anhydride are employed (e.g., when the
monomer ratio of styrene to maleic anhydride is 1:1 or 2:1), the amount of mercaptan used should be
increased in order to provide a lower molecular weight copolymer which will remain soluble in the solvent.
It is noted in the examples that when styrene and maleic anhydride were polymerized in 1,2-dichloroethane
with 2% 3-mercaptopropionic acid chain transfer agent, the resultant copolymer was insoluble in 1,2-
dichloroethane. When 3% of the mercaptan was employed, the resultant copolymer had a molecular
weight sufficiently low enough to remain in solution. It is therefore noted that consideration should be
taken when determining the amount of mercaptan to be used in the polymerization reaction to ensure
solubility. When a copolymer with a 1:1 ratio of styrene to maleic anhydride is to be made, a minimum
amount of about 3% mercaptan should be employed to ensure solubility- When a copolymer with a 9:1
ratio of styrene to maleic anhydride is to be made, as little as 0.5% mercaptan may be required.
As will be recognized by those skilled in the art, the copolymerization reaction may be conducted in any
number of ways. Styrene, maleic anhydride, and the mercaptan chain transfer agent may be
simultaneously added at slow rates to a reaction vessel containing 1,2-dichloroethane and catalyst at reflux
with agitation. The monomers and mercaptans may be dissolved first in 1,2-dichloroethane, if desired. An
alternative polymerzation method would be to simultaneously add only one monomer and mercaptan at
 0 119 414

slow rates to a reaction vessel which already contains the other monomer and catalyst in 1,2-
dichloroethane. The polymerization temperature in 1,2-dichlorethane is 70°—-100°C, with polymerization
preferably conducted between 80°— 95°C. The polymerization reaction proceeds rapidly at elevated
temperatures; therefore, a uniform reaction may only be achieved by slow addition of the monomers such
5 that the rate of addition does not exceed the rate of conversion of the monomer to polymer. In the
laboratory, the addition takes place over a period of approximately 4 to 8 hours. After the addition is
complete, the reaction is held at reflux for an additional 1 to 2 hours to ensure completion of the
polymerization. The reaction should also be conducted in an oxygen-free atmosphere.
Upon completion of the polymerization reaction, the solution is cooled and the resultant copolymer
10 with a molecular weight range of 500 to 10,000 will remain in solution in 1,2-dichloroethane and be
substantially odorless. The copolymer may thereafter be conveniently sulfonated as is, eliminating
intermediate recovery and handling steps. If a sulfonated copolymer is not desired, the copolymer may be
recovered after polymerization by conventional techniques such as dichloroethane distillation or by
addition of a non-solvent for the copolymer including various aliphatic or aromatic hydrocarbon solvents
15 which precipitate the copolymer.
The copolymer may be sulfonated by a variety of methods known to those skilled in the art. Generally,
a sulfonating agent is added on an equimolar basis with the styrene concentration of the copolymer in
order to monosubstitute each aromatic ring. Sulfur trioxide or other sulfur-containing materials capable of
rendering S03 available for sulfonating can be used. Use of sulfur trioxide as the sulfonating agent is
20 preferred. In order to prevent undesirable cross-linking of the aromatic rings of the copolymer and to
reduce the exothermic reactivity of the reagent, the use of a complex of sulfur trioxide and an organic
compound is suggested. See US—A—3,072,619 (cited previously) which describes the use of such S03-
organic complexes. Sulfur trioxide and/or the complexed sulfur trioxide may be dissolved in 1,2-
dichloroethane and then reacted with the copolymer by any conventional addition procedure. The
25 sulfonation reaction should be conducted under anhydrous conditions with cooling to temperatures of 0° to
50°C. and preferably from 10° to 30°C. As the sulfonation proceeds, the sulfonated polymer will precipitate
from solution.
Upon completion of the sulfonation reaction, the sulfonated copolymer should be neutralized
sufficiently with an appropriate base, e.g. sodium carbonate, in order to stabilize the acidic sulfonated
30 copolymer. After neutralization, the product may be recovered by conventional means including decanting,
filtration, or centrifuging. If desired, water may be added directly to the dichloroethane solution containing
the precipitated sulfonated copolymer without neutralization, whereby the water-soluble copolymer in free
acid for can be phase separated from the organic dichlorethane phase. In both cases, residual trace
amounts of dichloroethane may be removed by distillation.
35 In the following examples, all parts and percentages are given by weight and all temperatures are in
degrees Celsius unless otherwise noted.

Intrinsic Viscosity Measurement

40 The measurement of intrinsic viscosity (I.V.) of polymers is used in order to determine the relative
molecular weights of such polymers. The intrinsic viscosity of the styrene-maleic anhydride copolymers of
the present invention is measured employing the following test procedure.
Polymer solutions in dichloroethane in concentrations of approximately 5 g/dl, 2.5 g/dl, and 1./25 g/dl
are prepared. If the polymers are insoluble in 1,2-dichloroethane, tetrahydrofuran is used as a suitable
45 solvent. The flow rate(tc) of each polymer solution is measured as well as that of a solvent blank (t0) at25°C.
with a Cannon-Fenske viscometer. The reduced viscosity (r)) of the polymer solutions is calculated by the
following equation:

tofto - 1
50 Tired =
C

where tc = flow rate of polymer solution in seconds and c = actual concentration of polymer solution in g/
dl. The reduced viscosity values are then plotted versus the polymer concentrations of the solutions. The
55 I.V. of a polymer is obtained by extrapolating the line of the graph to c=0. Thus I.V. = n.red at c=0. As a
useful approximation an I.V. of 0.05 correlates to a molecular weight of 1,500 and an I.V. of 0.09 correlates
to a molecular weight of 7,000.

Example 1
60 This example demonstrates the effectiveness of 3-mercaptopropionic acid and methyl-3-
mercaptopropionate as chain transfer agents in the process herein. A series of styrene-maleic anhydride
(1:1) copolymers were prepared using various mercaptan chain transfer agents.
A mixture of 400 grams of 1,2-dichloroethane (DCE) and 4 grams of azoisobutyronitrile (AIBN) were
charged to a two-liter multiple-neck round bottom flask equipped with a stirrer, thermometer, condenser,
65 addition funnels and nitrogen inlet. With constant agitation, the mixture was heated to reflux (about 85°C)

4
 0 119 414
under nitrogen sweep and held at reflux for five minutes. Using three addition funnels, a mixture of 820
grams of DCE and 196 grams of maleic anhydride (2.0 mole); 208 grams of styrene (2.0 mole); and a
mixture of 200 grams of DCE, 20 grams of AIBN and an appropriate amount of mercaptan specified in Table
1 were simultaneously added over a period of six hours at reflux. Upon completion of the slow addition, the
mixture was refluxed for an additional one hour before cooling. The following data was recorded as found
in Table I.
It is evident that only the coupler samples G and H made with 3% of 3-mercaptopropionic acid and
methyl-3-mercaptopropionate produced low molecular weight polymers (low I.V.) which remained in
solution and possessed very weak mercaptan odors. Copolymer F, made with only 2% of 3-
mercaptopropionic acid, possessed only a low mercaptan odor; however, the molecular weight of the
copolymer was not sufficiently low enough to render it soluble in DEC. The only other soluble copolymer
(sample E) possessed an unacceptably high mercaptan odor.

Example 2
This example illustrates the preparation of a 3:1 styrene-maleic anhydride copolymer using 3-
mercaptopropionic acid as the chain transfer agent. A mixture of 312 grams of styrene, 15 grams of maleic
anhydride and 720 grams of DCE were charged to a two liter multiple-neck round bottom flask equipped
with a stirrer, thermometer, condenser, addition funnels and nitrogen inlet. With constant agitation, the
mixture was heated to reflux (about 91°C) under nitrogen sweep. Ten percent (10%) of a mixture of 300
grams of DCE, 16 grams of AIBN and 4 grams of 3-mercaptopropionic acid (0.97% based on weight of
monomers) was added to the flask and the mixture was held at reflux for five minutes. The remaining 90%
of the mixture was simultaneously added over a 4.25 hour period to the reaction flask with a mixture of 93
grams of maleic anhydride and 300 grams of DCE. At the end of the slow addition, the reflux temperature
had dropped to 85°C. The mixture was held at reflux for two hours after addition before cooling. A clear
polymer solution without any noticeable mercaptan odor was obtained. The I.V. of the polymer in DCE was
0.076 dl/g.

Example 3
The procedure of Example 1 was repeated employing a-methyl styrene and maleic anhydride
monomers in a 1:1 molar ratio with 2.3% (based on weight of the monomers) of 3-mercaptopropionic acid
as chain transfer agent. The resultant polymer did not possess a noticeable odor and was completely
soluble in DCE. The polymer had an i.V. in DCE of 0.053 dl/g.

Example 4
Copolymers of vinyl toluene and maleic anhydride in various molar ratios specified in Table 2 were
prepared with 3-mercaptopropionic acid as chain transfer agent. Sample J was prepared by the procedure
of Example 1. Samples K through 0 were prepared by the procedure of Example 2. All of the resultant
polymer solutions were clear and did not possess any noticeable mercaptan odor.

Example 5
This example illustrates the sulfonation of 1:1 styrene-maleic anhydride copolymer G in DCE of
Example 1.
A five-liter Morton flask equipped with a stirrer, thermometer, additional funnels, condenser with
drying tube and a gas inlet adapter was purged with nitrogen for 15 minutes. A mixture of 1125 grams of
DCE and 29 grams of triethy Iphosphate (0.1578 mole) was then added to the flask. With agitation, 12.9
grams of sulfur trioxide (0.1608 mole) was added slowly to form a 1:1 molar complex with the
triethylphosphate. The temperaature of the mixture was maintained at 15°—20°C. during the addition.
Using two addition funnels, 1050 ml of copolymer G solution
 Z
O
>—*
I—

ig 2 <U u <u <u &

O I— 3 3 = I 3 ^ - = J ' —
a. r - r - ^ - - O r0r - S3 - 3S
O _ J 0 0 0 0 3
° m c c c c o = o o
S 1- •>- T- U> <" ««
^ -I
O

UJ
o
cc
o
>-
@x.
z
<
y cm *
y ^ J S c X j r - ^ t ^ l D i n 3
-« 3 5 - | ^ i O O O O O O O
UJ i _ i | o o o o o o o o ±-
co z i?
< uj ^
1— Qi s_
>: @>"-

H- i_ -O T3 T3 C 3
C3 flj rB « Q. £e
5I— < o
uj -oo o u t -
g S c o = = = = $
u~ (T3 fa o tj o o +-> •<-
o; oo +@> •-- +J -r- -r- a. (fl
UJ Z o_ CJ CL O. CL CL "3 O
Jt; S o +-> s- u s- s_ t . . < / i

£*^ ^ c o a. a. o. n e o
2 r- +@* <0 i— « <0 I O-r-
a. o u u e </>
2 5 @
jj >, !o t.
>,
+? s- s- i—
>, 2 =
-r- |_ T3 S- E .O 5 S TT i
tJ UJ - O S f M C r O O E O C
< « s« S« »« S« S« *S £S
£ a! -
< 5 -
* .5"

@a

j 03 >-«

(/) — @
—@

6
 3 119 414
and 129.6 grams or suirur trioxide (1.6175 mole) were added simultaneously while maintaining the
:emperature of 15°— 20°C. during the sulfonation. The copolymer solution which contained 300 grams of
copolymer (1.5779 mole of styrene in copolymer) in DCE was added at a rate of 15 ml/minute. The sulfur
xioxide was added at a rate of 1 ml/minute. The sulfonated polymer precipitated as it formed. After
completing the sulfonation, 260 grams of anhydrous sodium carbonate was added to neutralize the
Dolymer. The polymer was filtered and then dried at 60°C. The resultant polymer dissolved completely in
water to give a yellowish solution which possessed no noticeable mercaptan odor.

Example 6
The procedure of Example 5 was repeated except that after completing the sulfonation, 1500 grams of
H20 was added to dissolve the sulfonated polymer. The aqueous layer was separated from DCE with a 2-
iter separatory funnel. The residual DCE in the aqueous solution was stripped by rotary evaporation under
@educed pressure. The final solution of the polymer in acid form was yellowish and possessed no
noticeable mercaptan odor.

Example 7 (Comparative)
Copolymer E (1:1 styrene-maleic anhydride copolymer employing n-butyl mercaptan chain transfer
agent) of Example 1 was sulfonated as described in Example 5. The resultant polymer possessed a strong
abjectionable mercaptan odor.
 E
in
-—• «
3C
—(
I—. u
0 •>-
< j=
2
Z
l— O t~- us ur> ey
Zi-.i^.'d-ioQoaoco i—
d.
UJ Q_ •
O O C M r - * 0 0 0 0 s
as cs: <o
a. o 4-
t— O
Q. <•-
<C
CM O +@>
01 CL
1Ij11 111 «
s <->
as i
< <r> X
(- <U
UJ
o
a
c
@a
il
<>
aUJ s-
i-t 3
OS (/l
1 1

O i-
O •—' V)
O
H kl
M U
1- _J
I- o
< eC . UI
O i S ^ ^ » - < r H r H r H </> •r-
4- >
c ;i u j ^ - i oj fO ro
m co i—i a>
< zZ sS uU
-I Ui VO O i-
oO = 13> C </>
£ _l oO =
O E
_1 o c
>- +-> i- c•
1-
z </» ra
i/i
_ jz
JZ
5» OJ i- i- 3
•r-
I:1: "ct o
s-
C r- "O
O "O >,
"O
T 3 ra
0) • t-
<> / > +->
UJ
uj ra
fa @< 01u
a.
2STT ' - 3 i i£
^ — —i1 sS z Zo O — -—
<<;£ rr-l1
— CM
U1 — •

8
 0 119 414

Claims

1. A process for preparing a copolymer of styrene and maleic anhydride in the molecular weight range
of 500 to 10,000 by polymerizing styrene and maleic anhydride monomers in a molar ratio of 1:1 to 9:1 in
5 1,2-dichloroethane at 70°— 100°C in the presence of a free radical generating polymerization catalyst and a
mercaptan chain transfer agent, characterized in that the polymerization is carried out in the presence of
0.5 —5%, based on the weight of the monomers, of 3-mercaptopropionic acid or methyl-3-
mercaptopropionic as the chain transfer agent, whereby a substantially odorless copolymer which remains
soluble in the 1,2-dichloroethane results.
10 2. The process of Claim 1, characterized in that the polymerization is carried out at 80° —95°C in the
presence of azoisobutyronitrile or 2,2-azobis (2-methyl-pentanenitrile) as the catalyst and 1—3% of the
chain transfer agent, whereby the copolymer has a molecular weight of from 1,000 to 4,000.
3. The process of Claim 1, characterized in that said molar ratio of styrene to maleic anhydride is 1:1 to
3:1.
'5 4. The process of Claim 1, characterized in that the styrene is a-methyl styrene or vinyl toluene.
5. The process of Claim 1, characterized in that the copolymer is recovered' by distilling off the
dichloethane solvent.
6. A process for preparing a sulfonated copolymer of styrene and maleic anhydride by polymerizing
styrene and maleic anhydride monomers in a molar ratio of 1:1 to 9:1 in 1,2-dichloroethane at 70° —100°C.
20 in the presence of a free radical generating polymerization catalyst and a mercaptan chain transfer agent
yielding a copolymer in the molecular weight range of 500 to 10,000, sulfonating the resulting copolymer in
the 1,2-dichloroethane, and recovering the resultant precipitated sulfonated copolymer, characterized in
that the polymerization is carried out in the presence of from 0.5 —5%, based on the weight of the
monomers, of 3-mercaptopropionic acid or methyl-3-mercaptopropionate, whereby a substantially
25 odorless and soluble copolymer of styrene and maleic anhydride is formed and results in a substantially
odorless copolymer after sulfonation.
7. The process of Claim 6, characterized in that the polymerization is carried out at 80° —95°C in the
presence of azoisobutyronitrile or 2,2'-azobis (2-methyl-pentanenitrile) as the free radical generating
polymerization catalyst and 1—3% of the chain transfer agent using a 1:1 to 3:1 molar ratio of styrene to
30 maleic anhydride, whereby the copolymer prior to sulfonation has a molecular weight of from 1,000 to
4,000.
8. The process of Claim 6, characterized in that the styrene is a-methyl styrene or vinyl toluene.
9. The process of Claim 6, characterized in that the sulfonated copolymer is neutralized with sodium
carbonate and recovered by filtration.
35 10. The process of Claim 6, characterized in that water is added after sulfonation such that the
sulfonated copolymer dissolved in the water and is separated and recovered in aqueous phase from the
dichloroethane.

Patentanspriiche
40'
1. Verfahren zur Herstellung eines Styrol-Maleinsaureanhydrid-Copolymers in dem
Molekulargewichtsbereich von 500 bis 10.000 durch Polymerisieren von Styrol- und Maleinsaureanhydrid-
Monomeren in einem Molverhaltnis von 1:1 bis 9:1 in 1,2-Dichlorethan bei 70 bis 100°C in Gegenwart eines
freie Radikaie bildenden Polymerisationskatalysators und eines Mercaptan-Kettenubertragers, dadurch
45 gekennzeichnet, daS die Polymerisation in Gegenwart von 0,5 bis 5%, bezogen auf das Gewicht der
Monomeren, an 3-Mercaptopropionsaure Oder Methyl-3-mercaptopropionate als Kettenubertrager
durchgefuhrt wird, wodurch ein im wesentlichen geruchloses Copolymer entsteht, das in 1,2-Dichlorethan
loslich bleibt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dalS die Polymerisation bei 80 bis 95°C in
so Gegenwart von Azoisobuttersaurenitril oder von 2,2'-Azobis(2-methyl-pentannitrii) als Katalysator und von
1 bis 3% Kettenubertrager durchgefuhrt wird, wodurch das Copolymer ein Molekulargewicht von 1.000 bis
4.000 aufweist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dal3 das Molverhaltnis von Styrol zu
Maleinsaureanhydrid 1:1 bis 3:1 betragt.
55 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, da(S das Styrol a-Methylstyrol oder Vinyltoluol
ist.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dalS das Copolymer durch Abdestillieren des
. Dichlorethanlosungsmittels wiedergewonnen wird.
6. Verfahren zur Herstellung eines sulfonierten Styrol-Maleinsaureanhydrid-Copolymers durch
60 Polymerisieren von Styrol- und Maleinsaureanhydrid-Monomeren in einem Molverhaltnis von 1:1 bis 9:1
in 1,2-Dichlorethan bei 70 bis 100°C in Gegenwart eines freie Radikaie bildenden
Polymerisationskatalysators und eines Mercaptan-Kettenubertragers was ein Copolymer in dem
Molekulargewichtsbereich von 500 bis 10.000 liefert, durch Sulfonieren des erhaltenen Copolymers in 1,2-
Dichlorethan und durch Wiedergewinnen des erhaltenen, ausgefallten sulfonierten Copolymers, dadurch
65 gekennzeichnet, dalS die Polymerisation in Gegenwart von 0,5 bis 5%, bezogen auf das Gewicht der

9
 0 119 414

Monomeren, an 3-Mercaptopropionsaure oder Methyl-3-mercaptopropionat durchgefuhrt wird, wodurch

ein im wesentlichen geruchioses und losliches Styrol-Maleinsaureanhydrid-Copolymer gebildet wird und
nach der Sulfonierung ein im wesentlichen geruchioses Copolymer anfallt.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daS die Polymerisation bei 80 bis 95°C in
5 Gegenwart von Azoisobuttersaurenitril oder 2,2'-Azobis(2-methyl-pentannitril) als der freie Radikaie
bildende Polymerisationskatalysator und von 1 bis 3% Kettenubertrager durchgefuhrt wird, wobei ein
Molverhaltnis von Styrol zu Maleinsaureanhydrid von 1:1 bis 3:1 gewahlt wird, wodurch das Copolymer
vor dem Sulfonieren ein Molekulargewicht von 1.000 bis 4.000 aufweist.
8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dalS das Styrol a-Methylstyrol oder Vinyltoluol
to ist.
9. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dalS das sulfonierte Copolymer mit
Natriumcarbonat neutralisiert und durch Filtrieren wiedergewonnen wird.
10. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dalS nach dem Sulfonieren derartig Wasser
zugegeben wird, dalS sich das sulfonierte Copolymer in Wasser lost, es von dem Dichlorethan abgesondert
is und in der walXrigen Phase wiedergewonnen wird.

Revendications

1. Procede pour preparer un copolymere de styrene et d'anhydride maleique dont le poids moleculaire
20 est compris dans la plage de 500 a 10.000, par polymerisation de monomeres de styrene et d'anhydride
maleique selon un rapport molaire de 1:1 a 9:1 dans du 1,2-dichloroethane a 70° —100CC en la presence
d'un catalyseur de polymerisation engendrant un radical libre et d'un agent de transfert de chaTne a base de
mercaptan, caracterise en ce que la polymerisation est realisee en la presence de 0,5 a 5%, sur la base du
poids des monomeres, d'acide-3-mercaptopropionique ou de methyl-3-mercaptopropionate en tant
25 qu'agent de transfert de chaTne, d'ou il resulte un copolymere sensiblement sans odeur qui reste soluble
dans le 1,2-dichloroethane.
2. Procede selon la revendication 1, caracterise en ce que la polymerisation est realisee a 80°C —95°C en
la presence d'azoisobutyronitrile ou de 2,2'-azobis (2-methyl-pentanenitrile) en tant que catalyseur et de
1—3% de I'agent de transfert de chaTne, le copolymere ayant un poids moleculaire compris entre 1.000 et
30 4.000.
3. Procede selon la revendication 1, caracterise en ce que ledit rapport molaire entre le styrene et
I'anhydride maleique est compris entre 1:1 et 3:1.
4. Procede selon la revendication 1, caracterise en ce que le styrene est du a-methylstyrene ou du
toluene vinylique.
35. 5. Procede selon la revendication 1, caracterise en ce que le copolymere est recupere par distillation a
partir du solvant dichloroethane.
6. Procede pour preparer un copolymere sulfone de styrene et d'anhydride maleique par
polymerisation de monomeres de styrene et d'anhydride maleique selon un rapport molaire de 1:1 a 9:1
dans du 1,2-dichloroethane a 70° —100°C en presence d'un catalyseur de polymerisation engendrant un
40 radical libre et d'un agent de transfert de chaTne a base de mercaptan donnant un copolymere dont le poids
moleculaire est compris dans la plage de 500 a 10.000, en sulfonant le copolymere resultant de styrene et
d'anhydride maleique dans le 1,2-dichloroethane, et en recuperant le copolymere sulfone precipite obtenu,
caracterise en ce que la polymerisation est realisee en la presence de 0,5 —5% base sur le poids du
monomere, d'acide-3-mercaptopropionique ou de methyl-3-mercaptopropionate en tant qu'agent de
45 transfert de chaTne, un polymere de styrene et d'anhydride maleique sensiblement sans odeur et soluble
etant ainsi forme et resultant apres la sulfonation en un copolymere sensiblement sans odeur.
7. Procede selon la revendication 6, caracterise en ce que la polymerisation est realisee a 80° —95CC en
la presence d'azoisobutyronitrile ou de 2;2'-azobis (2-methyl-pentanenitrile) en tant que catalyseur de
polymerisation engendrant un radical libre et de 1 a 3% d'un agent de transfert de chaTne, en utiiisant un
50 rapport molaire compris entre 1:1 et 3:1 entre le styrene et I'anhydride maleique, le copolymere ayant
avant sulfonation un poids moleculaire compris entre 1.000 et 4.000.
8. Procede selon la revendication 6, caracterise en ce que le styrene est du a-methylstyrene ou du
toluene vinylique.
9. Procede selon la revendication 6, caracterise en ce que le copolymere sulfone est neutralise avec du
55 carbonate de sodium et recupere par filtration.
10. Procede selon la revendication 6, caracterise en ce que de I'eau est ajoutee apres la sulfonation de
maniere que le copolymere sulfone se dissolve dans I'eau et soit separe et recupere en phase aqueuse
dudit dichloroethane.

60

65

10